Human or animal hair colourants comprising nitrobenzene dyes



U.S. Cl. 8-10 v formula;

United States Patent 3,446,567 HUMAN 0R ANIMAL HAIR'COLOURANTS COMPRISING NITROBENZENE DYES Horst Augustin, Mannheim, Neu-Ostheim, and Ralph Heringlake, Hamburg, Germany, assignors to -Lever Brothers Company,,New-York, N.Y., a corporation of Maine.

No Drawing. Filed Apr. 13, 1965, Ser. No. 447,866

Claims priority, application ggrmany, Apr. 14, 1964,

7 U 10, Int. Cl. D06p 3/04; A61k 7/12 ABSTRACT OF THE DISCLOSURE 4 Claims This disclosureis concerned with certain bis(beta-'hy- I I droxyalkyl)-amino-2-amino-4-nitro-benzene compounds which are yellow-orange dyestufis. This disclosure is also concerned with hair icolourants containing these yelloworange dyestuffs and certain blue-violet dyestuifs for dyeing previously treated hair to an even shade, i.e., a uni- .form'color.

This invention relatesto colourants for dyeing or tinting human or animal hair.

According to ,the invention'there is provided a new yellow-orange dyestutt for colouring hair having the where a i R and R represent hydroxyalkyl groups having 2 to 6 carbon atoms; and 1 R and R representhydrogen or alkylgroups having 1 to 4 carbon atoms.

R and R may be the same or ditferent and R and R may be the same or different.

Examples of the groups R and R are -CH CH OH, CH CH(OH)CH and CH CH(OH)CH OH.

The groups R and R may be methyl, ethyl, propyl or butyl groups.

The dyes of the inventionhave good fastness to light.

The yellow-orange dyes of the invention canbe obtained by converting 1-chloro-2,4-dinitrobenzene or its 5- and/or 6'alky1-substituted derivatives with hydroxyalkyl amines having the formula HN'R R where R and R have the above meanings, and partially reducing the corresponding reaction products with, .for example, hydrogen sulphide or sodium polysulphide.

It has been found that when blue-violet dyestuffs of the formula are used in combination with the above yellow-orange dyestuffs good results are obtained, I H i f where R R R and R have the above meanings.

3,446,567 Pat nt a 27, 19 9 Accordingly the present invention also provides a hair colourant comprising a blue violet component having the formula and a'yellow orange component having the formula These hair colourants dye hair a uniform colour even verting 1,4-diamino-2-nitrobenzene or its 5- and/or 6- usually used in hair colourants.

centages are by weight.

form of a tinting agent when a part of the hair has been previously treated such as by permanent-waving or previous dyeing.

For example, if strands of white hair, half permanently waved, are dyed with solutions containing equal parts of the blue-violet and yellow-orange dyes. ofthe above formulae, natural blonde and brown shades are obtained 'depending on the concentration of the dyes, the differ- 35' ence between the permanently waved and the untreated parts being apparent only in the somewhat dilferent intensity of the dye, but not in any substantial diifere'nce in the shade. Further, the above combination of dyes gives shades having good fastnessto light.

The above blue-violet dyes can be prepared by conalkyl-substituted derivatives with hydroxyalkyl halides to the 1,4-di-substituted compounds.

The hair colourants of the invention may also contain other direct dyes, as well as other components The hair colourants of the invention may be in the such as, for example, a hair rinse or colour shampoo. i t

The following examples illustrate the invention. Per- Example 1 ducing hydrogen sulphide into a stirred amoniacal-alcoholic solution of the compound as the temperature of the solution was raised to the boiling point.

After evaporation of the solution, the residue was suspended in 2 N HCl, sulphur filtered oil, and the dye- 'stnif was precipitated by the addition of sodium hy' 'droxide solution. Upon recrystallisation from water bis- ,(betawhydroxyethyl)-amino-2-amino-4-nitro-benzene was obtained asa yellow-orange solid having a melting point This compound gave, on dyeing hair, a yellow-orange shade having good fastness to light.

The compound was found to have a light fastness superior to that of the yellow dyestufl? l-(beta-hydroxyethyl) -amino-'2-amino-4-nitro-benzene.

Example 2 N-(beta-hydroxyethyl) N (beta hydroxypropyl)- amino-2-amino-4-nitro-benzene was prepared in a manner similar to that described in Example 1, ethanol-isopropanol-amine being used instead of diethanolamine. 'Further, the partial reduction was carried out with sodium polysulphide instead of hydrogen sulphide.

The compound obtained had a melting point of 126 C. (A =395 mu; e=4990).

CHzCHaOH Example 3 Bis-(beta-hydroxypropyl)-amino 2 amino 4 nitrobenzene was prepared in a manner analogous to that referred to in Example 2, using di-isopropanolamine instead of ethanol-isopropanol-amine.

The compound obtained had a melting point of 114-115 C. (M :400 ma; e=4770).

Example 4 0.5 g. of 1,4-di-(beta-hydroxyethylamino)-2-nitro-benzene and 0.5 g. of bis-(beta-hydroxyethyl)-amino-2- amino-4-nitro-benzene were dissolved in a mixture of 96 g. of water, 2 g. of triethanolamine and 1 g. of a wetting agent. This solution dyed strands of white hair, half permanently waved, an even natural brown shade in 20 minutes at 30 C.

In order to demonstrate the good results obtained with the combination of dyes of the invention comparative experiments A and B described below were carried out.

Comparative Experiment A Percent Blue-violet dye 0.5 Yellow-orange dye 0.5 Wetting agent (sodium alkyl sulphonate) 1.0 Dipropylenetriamine 2.0 Water to 100.0

The above compositions were used to dye strands of white hair, half permanently waved, by treatment for 20 minutes at room temperature.

The mixture containing as the yellow-orange component bis-(beta-hydroxyethyl')-amino-2-amino-4-nitro benzene dyed the hair an even natural brown colour with only a slight difierence in intensity of colour between the waved and unwaved portions of the hair.

In contrast to this, with the hair dyed using the other composition there was a marked difference in the shades produced on the two halves of the hair.

4 Comparative Experiment B In this comparative experiment two compositions consisting of Percent Blue-violet dye 0.5 Yellow-orange dye 0.5 Wetting agent (sodium alkyl sulphonate) 1.0 Dipropylenetriamine 2.0 Water to 100.0

were again employed and the compositions were used to dye strands of white hair, half permanently waved, by treatment at 30 C. for 20 minutes.

In each case the blue-violet dye was the same as employed in Comparative Experiment A.

In one case the yellow-orange dye was bis-(beta-hydroxyethyl)-amino-2-amino-4-nitro-benzene and in the other it was 1,2-di-(beta-hydroxyethylamino)-4-nitrobenzene.

The composition containing as the yellow component bis-(beta hydroxyethyl) amino 2 amino 4 nitrobenzene gave very noticeably better results. The hair was dyed with the composition containing this dyestuff an even natural brown shade; there was a slight difference in intensity of shade between the two halves of the hair.

In contrast to this result the other composition dyed the hair an unnatural and less even brown colour.

These experiments show the superior results obtained when the yellow-orange component has two hydroxyalkyl groups which are both attached to the same nitrogen atom.

Other experiments similar to Comparative Experiment B were carried out using as the yellow-orange component the dyes Acid Orange 3( Colour Index Number: 10385), Acid Yellow 11 (Colour Index Number: 18820), and 2-amino-4-nitro-phenol. In none of these experiments was the hair dyed an even natural brown shade.

Still further experiments similar to Comparative Experiment B were carried out using as the blue-violet component the dyestutt l-bis-(beta-hydroxyethyl)-amino-4- (beta-hydroxyethyl)-amino-3-nitro-benzene and as the yellow-orange component Acid Orange 3, Acid Yellow 11, 2-amino-4-nitro-phenol, 1-(beta-hydroxyethylamino)- 2-amino-4-nitro-benzene, and bis-(beta hydroxyethyl)- amino-2-amino-4-nitro-benzene. Again in no case was the hair dyed an even natural brown shade.

What is claimed is:

1. A hair colourant comprising a blue-violet component having the formula IIIHR R NO:

I I'HR and a yellow-orange component being a dyestuif of the formula where in each formula R and R represent hydroxyalkyl having 2 to 6 carbon atoms; and R and R represent hydrogen or alkyl having 1 to 4 carbon atoms.

2. The hair colourant according to claim 1 in which the yellow-orange component is bis-(beta-hydroxyethyl)- amino-2-amino-4-nitro-benzene.

3. The hair colourant according to claim 1 in which the yellow-orange component is N-(beta-hydroxyethyl)- N-(beta-hydroxypropyl) -amino-2-amin'o-4-nitro-benzene.

4. The hair colourant according to claim 1 in which the yellow-orange component is bis-(beta-hydroxypropyD- amino-2-amino-4-nitro-benzene.

References Cited UNITED STATES PATENTS 6 FOREIGN PATENTS 805,746 12/1958 Great Britain.

OTHER REFERENCES 5 Heald: American Perfumer and Cosmetics, vol. 78, N0.

Marsc all 260573 X VERA c. CLARKE, Assistant Examiner. Eckardt 167-88 10 Eckardt 16788 us. (:1. X.R. Brunner 167-88 s 10.1 

